Article including light valves

ABSTRACT

An article, includes a layer including at least one color-rendering portion and at least one light valve; and a metal reflector portion, wherein the at least one light valve is positioned in the layer to provide reflection of incident light through the at least one light valve. A method of making an article is also disclosed.

FIELD OF THE INVENTION

The present disclosure generally relates to articles, such as opticaldevices in the form of foil, sheets, and/or flakes. The article caninclude a layer including at least one color-rendering portion and atleast one light valve; and a metal reflector portion; wherein the atleast one light valve is positioned in the layer to provide reflectionof incident light through the at least one light valve. Methods ofmaking the optical devices are also disclosed.

BACKGROUND OF THE INVENTION

A color-rendering layer contains colorant particles that can absorband/or scatter certain wavelengths of light. The absorption and/or thescattering of light in the color-rendering layer can completely obscurethe light from reaching a reflector layer. This results in an articlethat lacks a metallic sheen. For example, an opaque, such as black,color-rendering layer absorbs all visible light thereby preventing thelight from reaching the reflector layer underneath. Because the lightdoes not reach the reflector layer, it is not reflected, and the articledoes not produce a metallic sheen. As another example, an opaque, suchas white, color-rendering layer scatters light and can reach a level oflight scattering so that the light does not reach the reflector layer,it is not reflected, and the article does not produce a metallic sheen.

The strength of metallic sheen of an article, such as an optical device,for example, a special effect pigment, is determined by the amount oflight reflected by a reflector layer. An article whose reflector layeris fully covered by an opaque color-rendering layer is unable to reflectany incident light and therefore lacks any metallic sheen.

What is needed is an article that includes a layer including at leastone color-rendering portion and at least one light valve; and a metalreflector portion that can produce a metallic sheen under differinglighting conditions, such as diffuse lighting and direct lighting.

SUMMARY OF THE INVENTION

In an aspect, there is disclosed an article including a layer includingat least one color-rendering portion and at least one light valve; and ametal reflector portion; wherein the at least one light valve ispositioned in the layer to provide reflection of incident light throughthe at least one light valve.

In a further aspect, there is disclosed a method of making an articleincluding coating a first layer including at least one color-renderingportion and at least one light valve onto a substrate; depositing ametal reflector portion onto the first layer; and optionally coating asecond layer including at least one color-rendering portion having atleast one light valve onto the metal reflector portion.

Additional features and advantages of various embodiments will be setforth, in part, in the description that follows, and will, in part, beapparent from the description, or can be learned by the practice ofvarious embodiments. The objectives and other advantages of variousembodiments will be realized and attained by means of the elements andcombinations particularly pointed out in the description herein.

BRIEF DESCRIPTION OF THE DRAWINGS

The present disclosure in its several aspects and embodiments can bemore fully understood from the detailed description and the accompanyingdrawings, wherein:

FIG. 1A is a cross-section of an article including a layer including atleast one color-rendering portion and at least one light valve,according to an aspect of the present disclosure;

FIGS. 1B-1D are cross-sections of an article, according to other aspectsof the present disclosure;

FIGS. 2A-B are cross-sections of an article including a layer includingat least one color-rendering portion and at least one light valve,according to another aspect of the present disclosure;

FIG. 3A is a cross-section of an article including at least onecolor-rendering portion and at least one light valve, according toanother aspect of the present disclosure;

FIGS. 3B-3E are cross-sections of an article including a layer includingat least one color-rendering portion and at least one light valve,according to another aspect of the present disclosure;

FIG. 4A is a cross-section of an article including a layer including atleast one color-rendering portion and at least one light valve,according to an aspect of the present disclosure; and

FIGS. 4B-4D are cross-sections of an article including a layer includingat least one color-rendering portion and at least one light valve,according to another aspect of the present disclosure.

Throughout this specification and figures like reference numbersidentify like elements.

DETAILED DESCRIPTION OF THE INVENTION

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory only,and are intended to provide an explanation of various embodiments of thepresent teachings. In its broad and varied embodiments, disclosed hereinare articles, such as optical devices, for example, in the form offoils, sheets, and flakes; and a method of manufacturing the article. Asshown in FIGS. 1A, 2A, 3A, and 4A, the article 10 can include a layer 13including at least one color-rendering portion 14 and at least one lightvalve 12; and a metal reflector portion 16; wherein the at least onelight valve 12 is positioned in the layer 13 to provide reflection ofincident light through the at least one light valve 12. The at least onelight valve 12 is an optical channel through which incident light canreach the metal reflector portion 16.

A “light valve” 12 is a designed optical channel having a geometricshape, size, arrangement, distribution, and material properties. Thelight valve 12 can be used and placed within one or more layers of anarticle.

The light valve 12 can be located within a layer 13 having acolor-rendering portion 14 to enable incident light to reach thereflector portion 16 and the reflected light to transmit through thelight valve 12, as shown in FIG. 1A. A light valve 12 can control theamount, intensity, spectral composition, and direction of the incidentlight reaching the reflector portion 16. In an aspect, the light valve12 can control the amount, intensity, spectral composition, anddirection of the light reflected from the reflector portion 16. In afurther aspect, the light valve 12 can control the amount, intensity,and spectral composition of the scattered or absorbed light by thearticle 10.

A light valve 12 can be located within a transparent layer 20 to providean optical channel to a color-rendering portion 14 or a light scatteringlayer. The transparent layer 20 can be disposed on or external to acolor-rendering portion 14. The light valve 12 can enable incident lightto reach a color-rendering portion 14 or a light scattering layer andthe reflected and/or scattered light to transmit through the opticalchannel. In an aspect, a reflector portion 16 can be in the transparentlayer 20. The reflector portion 16 can form a boundary of the lightvalve 12.

In this manner, the light valve 12 can be used to tune an article 10,such as an optical device, for example a special effect pigment, thatincludes a light valve 12 and a reflector portion 16. In an aspect, thelight valve 12 can enhance a metallic sheen of the article 10, forexample under a diffuse lighting condition, and/or reduce a metallicsheen, for example under a direct lighting condition.

As shown in FIGS. 1A-1D, 2A, and 2B, the at least one light valve 12 canbe a void area in the layer 13. A void area can be an absence ofmaterial to create an empty space and thereby an optical channel.

The light valve 12 can be any dimension (size or shape) so long asincident light is allowed to pass through the light valve 12 to bereflected by a reflector portion 16. In an aspect, the at least onelight valve 12 is dimensioned to allow incident light to pass throughthe at least one light valve 12. Depending upon the dimension of the atleast one light valve 12 and the angle of the incident light, the amountof incident light that passes through the light valve 12 and isreflected by the reflector portion 16 may vary. For example, a largerdimensioned light valve 12 is more likely to allow incident light topass through and be reflected by the reflector portion 16, regardless ofthe angle of the incident light, as shown in FIG. 1A. Additionally, asmaller dimensioned light valve 12 is less likely to allow incidentlight to pass through and be reflected by the reflector portion 16, asshown in FIG. 1C.

The light valve 12 can have a width w and a height h, as shown in FIG.1B. The width w can be any size, but is less than an entire width of thelayer 13 that includes the at least one light valve 12. The width w canbe small enough so that the at least one light valve 12 is a pluralityof light valves 12 spaced throughout the layer 13. The height h of theat least one light valve 12 can be any size, but in most cases, can beat least the same height (if not greater than) as the layer 13. Inanother aspect, the at least one light valve 12 can extend through atleast a portion of a thickness (a portion of a height) of the layer 13.

The at least one light valve 12 can be a three-dimensional shape withflat polygonal or circular faces. As shown in FIGS. 1A-1D, the at leastone light valve 12 can be a three-dimensional polygon, such as a square,diamond, or rectangle. The at least one light valve 12 can be athree-dimensional column. The three-dimensional shape of the at leastone light valve 12 can be a void area. The three-dimensional shape ofthe at least one light valve 12 can be the same height as the layer 13or can extend beyond a height of the layer 13.

As shown in FIGS. 1B, 3C-3E, 4C, and 4D, a plurality of light valves 12can be present in the layer 13, such as a first layer 13 and a secondlayer 13′. In an aspect, a light valve 12 can be adjacent to acolor-rendering portion 14 on a first side and adjacent to a metalreflector portion 16 on another side. In the instance of a plurality oflight valves 12, they can be present in a random pattern or in adesigned pattern, such as an array.

In another aspect, as shown in FIGS. 2A-2B, the at least one light valve12 can be a void area around a three-dimensional shape, such as theround shape of the metal reflector portion 16.

As shown in FIGS. 2A-2B, a portion of the at least one light valve 12can extend above a surface of the layer 13. In this manner, a metallicsheen of the article 10 can be increased, such as during exposure todiffuse lighting (e.g., cloudy day), because a portion of incident lightcan become collimated. Under certain lighting conditions, the amount andthe direction of reflected light can be determined by the curvature (thediameter) of the curved metal reflector 16 and the exposed area of thecurved metal reflector 16 above a surface of the layer 13. When a director a collimated light is shone on the curved metal reflector 16, thereflected light becomes divergent, implying reduced sheen from thearticle 10. In the case where the article 10 is shone by a directincident light perpendicular to the surface, i.e., at 0 degrees incidentangle, the majority of the light is reflected off the curved metalreflector 16 at various angles depending on the reflecting location onthe curved metal reflector 16. This indicates that there is less amountof reflection and hence less sheen along the normal direction.

As shown in FIGS. 3A-3E, the at least one light valve 12 can be atransparent material. The refractive index of the transparent materialcan affect the angles of the incident and reflected light passingthrough the at least one light valve 12. The transparent material canhave any dimension discussed above. In an aspect, as shown in FIGS.3A-3E, the at least one light valve 12 can be a three-dimensional roundshape, such as a bead. For example, the at least one light valve 12 canbe a bead of a transparent material with a defined geometry that isincluded within the layer 13, such as the first layer 13 and the secondlayer 13′. The at least one light valve 12 can be a bead chosen frompolystyrene and silica. A diameter of the bead can be greater than orequal to a height of the layer 13, such as the first layer 13 and/or thesecond layer 13′. Non-limiting examples of the transparent materialinclude a clear resin, polystyrene, polyvinyl acetate, polyacrylates,polymethacrylates, polyurethanes, polyesters, polycarbonates,polyamides, polyimides, polyvinyl chloride, silicones, epoxy resins.

In an aspect, the beads can be dissolved by a solvent to form a voidarea (e.g., an air-filled area). For example, after construction of thearticle 10, the beads can be dissolved by a solvent, such as water. Thevoid areas can then be filled with a transparent resin. In anotheraspect, the beads can be polystyrene, which can be dissolved by tolueneto form the light valves 12.

The article 10, as shown in the Figures, can include a metal reflectorportion 16. The metal reflector portion 16 can be dimensioned to reflectlight through the at least one light valve 12 present in the layer 13.In an aspect, the metal reflector portion 16 can be a layer, as shown inFIGS. 1A-1D and 3A-4D. The metal reflector portion 16 can be adjacent toat least one light valve 12, such as a plurality of light valves 12. Themetal reflector portion 16 can be in a layer and between at least onelight valve on a first surface and on a second surface. In this manner,at least one light valve 12 can pass light through to the metalreflector portion 16 on either surface of the metal reflector portion16.

In another aspect, the metal reflector portion 16 can be a sphericalshape, as shown in FIGS. 2A-2B. The metal reflector portion 16 can be atleast one curved metal reflector 16, such as a plurality of curved metalreflector portions 16. The plurality of curved metal reflector portions16 can be present in the layer 13. Each curved metal reflector portion16 of the plurality of curved metal reflector portions 16 can besurrounded by at least one light valve 12.

The metal reflector portion 16 can be a metal and/or metal alloy. In anaspect, the material for the metal reflector portion 16 can include anymaterials that have reflective characteristics. An example of areflector material can be aluminum, which has good reflectancecharacteristics, is inexpensive, and easy to form into or deposit as athin layer. However, other reflector materials can also be used in placeof aluminum. Non-limiting examples of material suitable for the metalreflector portion 16 include aluminum, zinc, steel, copper, silver,gold, platinum, palladium, nickel, cobalt, niobium, chromium, tin, andcombinations or alloys of these or other metals, such as bronze, brass,and stainless steel. Other useful reflector materials include, but arenot limited to, the transition and lanthanide metals and combinationsthereof.

The article 10, as shown in the Figures, can include at least onecolor-rendering portion 14 in the layer 13. The at least onecolor-rendering portion 14 can be designed in dimension (size or shapeor directionality) so long as visible color is provided to the article10. For example, as shown in FIGS. 1A-1D, the color-rendering portion 14can be a three-dimensional shape with flat polygon faces. In anotheraspect, as shown in FIGS. 2A-3E, the color-rendering portion 14 can behourglass-shaped and/or flat on one-side and concave on another. Inanother aspect, as shown in FIGS. 4A-4D, the color-rendering portion 14can be a three-dimensional spherical shape. For example, thecolor-rendering portion 14 can be a bead. In another aspect, thecolor-rendering portion 14 can be a continuous coating layer in whichlight valves 12 are distributed.

In an aspect, the at least one color-rendering portion 14 can be opaque,for example, white, black or any visible color. In an aspect, the atleast one color-rendering portion 14 can include light absorbingmaterials or light scattering materials. The at least onecolor-rendering portion 14 can include at least one of dyes, pigments,and colorants. The color-rendering portion 14 can be white and caninclude, but is not limited to, TiO₂, BaSO₄, ZnS, white pigments, orwhite colorants. The color-rendering portion 14 can be black and caninclude, but is not limited to, carbon black, acid black 194, acid black234, reactive black 8, reactive black 31, solvent black 5. Thecolor-rendering portion 14 can be any pigment, such as an organicpigment, including, but not limited to, Pigment Red 254, Pigment Red264, Pigment Blue 60, Pigment Blue 15, Pigment Orange 73, Pigment Yellow194, Pigment Red 202, Pigment Red 122, Pigment Red 179, Pigment Red 170,Pigment Red 144, Pigment Red 177, Pigment Red 255, Pigment Brown 23,Pigment Yellow 109, Pigment Yellow 110, Pigment Yellow 147, PigmentYellow 74, Pigment Yellow 83, Pigment Yellow 13, Pigment Yellow 191.1,Pigment Orange 61, Pigment Orange 71, Pigment Orange 48, Pigment Orange49, Pigment Violet 23, Pigment Violet 37, Pigment Violet 19, PigmentGreen 7, Pigment Green 36, and mixtures thereof. Non-limiting examplesof inorganic pigments suitable for use in the color-rendering portion 14include carbon black, metal oxides, mixed metal oxides, antimony yellow,lead chromate, lead chromate sulfate, lead molybdate, ultramarine blue,cobalt blue, manganese blue, chrome oxide green, hydrated chrome oxidegreen, cobalt green, metal sulfides, cadmium sulfoselenides, zincferrite, and bismuth vanadate, and mixtures thereof. The at least onecolor-rendering portion 14 can be water insoluble.

As shown in FIGS. 1C, 1D, 2B, 3B, 3D, 3E, 4B, and 4D, the article 10 canfurther include a transparent layer 20. The transparent layer 20 can beincluded on any exterior surface of the article 10. For example, asshown in FIGS. 1C, and 3E, the transparent layer 20 can be adjacent tothe metal reflector portion 16 and, as shown in FIGS. 1D, 3B, 3D, 3E,4B, and 4D the transparent layer 20 can be adjacent the layer 13. In anaspect, more than one transparent layer 20, 20′, 20″, and 20″′ can bepresent in the article 10. The transparent layer 20 can provide a levelsurface to the article 10. The transparent layer 20 can be formedmaterials a clear resin, polyacrylates, polymethacrylates, polystyrene,polyvinyl acetate, polyurethanes, polyvinyl chloride, polyvinyl alcohol,polyesters, polycarbonates, polyamides, polyimides, silicones, epoxyresins, their copolymers, etc. The article 10 can include a layer 13,such as a first layer 13 and/or a second layer 13′. The first layer 13can be the same or different from the second layer 13′ in terms ofcolor, dimension, type of materials, number of light valves 12, etc. Asshown in FIGS. 1B, 3C-3E, and 4C-4D, the article 10 can include a firstlayer 13 and a second layer 13′ with a metal reflector portion 16therebetween. The layer 13 can include at least one color-renderingportion 14 and at least one light valve 12.

The layer 13 can be a selective light modulator layer (SLML). The SLMLis a physical layer comprising a plurality of optical functions aimingat modulating (absorbing and or emitting) light intensity in different,selected regions of spectrum of electromagnetic radiation withwavelengths ranging from about 0.2 μm to about 20 μm. The SLML canselectively modulate light by means of absorption provided by aselective light modulator system (SLMS) (discussed in more detailbelow). In an aspect, the article 10 can include a SLML that selectivelyabsorbs specific wavelengths of energy, such as light.

A SLML (and/or the materials within the SLML) can selectively modulatelight. For example, an SLML can control the amount of transmission inspecific wavelengths. In some examples, the SLML can selectively absorbspecific wavelengths of energy (e.g., in the visible and/or non-visibleranges). For example, the SLML can be a “colored layer” and/or a“wavelength selective absorbing layer.” In some examples, the specificwavelengths absorbed can cause the article to appear a specific color.For example, the SLML can appear red to the human eye (e.g., the SLMLcan absorb wavelengths of light below approximately 620 nm and thusreflect or transmit wavelengths of energy that appear red). This can beaccomplished by adding selective light modulator particles (SLMP) thatare colorants (e.g., organic and/or inorganic pigments and/or dyes,) toa host material, such as a dielectric material, including but notlimited to a polymer. For example, in some instances, the SLML can be acolored plastic.

In some examples, some or all of the specific wavelengths absorbed canbe in the visible range (e.g., the SLML can be absorbing throughout thevisible, but transparent in the infrared). The resulting article wouldappear black, but reflect light in the infrared. In some examplesdescribed above, the wavelengths absorbed (and/or the specific visiblecolor) of the article and/or SLML can depend, at least in part, on thethickness of the SLML. Additionally, or alternatively, the wavelengthsof energy absorbed by the SLML (and/or the color in which these layersand/or the flake appears) can depend in part on the addition of certainaspects to the SLML. In addition to absorbing certain wavelengths ofenergy, the SLML can achieve at least one of bolstering a reflectorportion against degradation; enabling release from a substrate; enablingsizing; providing some resistance to environmental degradation, such asoxidation of aluminum or other metals and materials used in a reflectorportion; and high performance in transmission, reflection, andabsorption of light based upon the composition and thickness of theSLML.

In some examples, in addition to or as an alternative to the SLMLselectively absorbing specific wavelengths of energy and/or wavelengthsof visible light, the SLML of the article can control the refractiveindex and/or the SLML can include selective light modulator particles(SLMPs) that can control refractive index. SLMPs that can control therefractive index of the SLML can be included with the host material inaddition to or as an alternative to an absorption controlling SLMPs(e.g., colorants). In some examples, the host material can be combinedwith both absorption controlling SLMPs and refractive index SLMPs in theSLML. In some examples, the same SLMP can control both absorption andrefractive index.

The performance of the SLML can be determined based upon the selectionof materials present in the SLML. In an aspect, the SLML can improve atleast one of the following properties: flake handling, corrosion,alignment, and environmental performance of any other layers withinarticle.

The SLML (including each SLML present in an article, if multiple layersare present) can each independently comprise a host material alone, or ahost material combined with a selective light modulator system (SLMS).In an aspect, at least one of the first SLML can include a hostmaterial. In another aspect, at least one of the first SLML can includea host material and a SLMS. The SLMS can include a selective lightmodulator molecule (SLMM), a selective light modulator particle (SLMP),an additive, or combinations thereof.

The composition of the SLML can have a solids content ranging from about0.01% to about 100%, for example from about 0.05% to about 80%, and as afurther example from about 1% to about 30%. In some aspects, the solidscontent can be greater than 3%. In some aspects, the composition of theSLML can have a solids content ranging from about 3% to about 100%, forexample from about 4% to 50%.

The host material of the first SLML can independently be a film formingmaterial applied as a coating liquid and serving optical and structuralpurposes. The host material can be used as a host (matrix) forintroducing, if necessary, a guest system, such as the selective lightmodulator system (SLMS), for providing additional light modulatorproperties to the article.

The host material can be a dielectric material. Additionally, oralternatively, the host material can be at least one of an organicpolymer, an inorganic polymer, and a composite material. Non-limitingexamples of the organic polymer include thermoplastics, such aspolyesters, polyolefins, polycarbonates, polyamides, polyimides,polyurethanes, acrylics, acrylates, polyvinylesters, polyethers,polythiols, silicones, fluorocarbons, and various co-polymers thereof;thermosets, such as epoxies, polyurethanes, acrylates, melamineformaldehyde, urea formaldehyde, and phenol formaldehyde; and energycurable materials, such as acrylates, epoxies, vinyls, vinyl esters,styrenes, and silanes. Non-limiting examples of inorganic polymersincludes silanes, siloxanes, titanates, zirconates, aluminates,silicates, phosphazanes, polyborazylenes, and polythiazyls.

The first SLML can include from about 0.001% to about 100% by weight ofa host material. In an aspect, the host material can be present in theSLML in an amount ranging from about 0.01% to about 95% by weight, forexample from about 0.1% to about 90%, and as a further example fromabout 1% to about 87% by weight of the SLML.

The SLMS, for use in the SLML with the host material, can eachindependently comprise selective light modulator particles (SLMP),selective light modulator molecules (SLMM), additives, or a combinationthereof. The SLMS can also comprise other materials. The SLMS canprovide modulation of the amplitude of electromagnetic radiation (byabsorption, reflectance, fluorescence etc.) in a selective region or theentire spectral range of interest (0.2 μm to 20 μm).

The first SLML can each independently include in an SLMS a SLMP. TheSLMP can be any particle combined with the host material to selectivelycontrol light modulation, including, but not limited to color shiftingparticles, dyes, colorants include colorant includes one or more of dyes(such as phthalocyanine-based compounds), pigments, reflective pigments,color shifting pigments, quantum dots, and selective reflectors.Non-limiting examples of a SLMP include: organic pigments, inorganicpigments, quantum dots, nanoparticles (selectively reflecting and/orabsorbing), micelles, etc. The nanoparticles can include, but are notlimited to organic and metalorganic materials having a high value ofrefractive index (n>1.6 at wavelength of about 550 nm); metal oxides,such as TiO₂, ZrO₂, In₂O₃, In₂O₃—SnO, SnO₂, Fe_(x)O_(y) (wherein x and yare each independently integers greater than 0), and WO₃; metalsulfides, such as ZnS, and Cu_(x)S_(y) (wherein x and y are eachindependently integers greater than 0); chalcogenides, quantum dots,metal nanoparticles; carbonates; fluorides; and mixtures thereof.

Examples of a SLMM include but are not limited to: organic dyes,inorganic dyes, micelles, and other molecular systems containing achromophore.

In some aspects, SLMS of the first SLML can include at least oneadditive, such as a curing agent, and a coating aid.

The curing agent can be a compound or material that can initiatehardening, vitrification, crosslinking, or polymerizing of the hostmaterial. Non-limiting examples of a curing agent include solvents,radical generators (by energy or chemical), acid generators (by energyor chemical), condensation initiators, and acid/base catalysts.

Non-limiting examples of the coating aid include leveling agents,wetting agents, defoamers, adhesion promoters, antioxidants, UVstabilizers, curing inhibition mitigating agents, antifouling agents,corrosion inhibitors, photosensitizers, secondary crosslinkers, andinfrared absorbers for enhanced infrared drying. In an aspect, theantioxidant can be present in the composition of the SLML in an amountranging from about 25 ppm to about 5% by weight.

The first SLML can each independently comprise a solvent. Non-limitingexamples of solvents can include acetates, such as ethyl acetate, propylacetate, and butyl acetate; acetone; water; ketones, such as dimethylketone (DMK), methylethyl ketone (MEK), secbutyl methyl ketone (SBMK),ter-butyl methyl ketone (TBMK), cyclopenthanon, and anisole; glycol andglycol derivatives, such as propylene glycol methyl ether, and propyleneglycol methyl ether acetate; alcohols, such as isopropyl alcohol, anddiacetone alcohol; esters, such as malonates; heterocyclic solvents,such as n-methyl pyrrolidone; hydrocarbons, such as toluene, and xylene;coalescing solvents, such as glycol ethers; and mixtures thereof. In anaspect, the solvent can be present in the first SLML in an amountranging from about 0% to about 99.9%, for example from about 0.005% toabout 99%, and as a further example from about 0.05% to about 90% byweight relative to the total weight of the SLML.

In some examples, the first SLML can include a composition having atleast one of (i) a photoinitiator, (ii) an oxygen inhibition mitigationcomposition, (iii) a leveling agent, and (iv) a defoamer.

The oxygen inhibition mitigation composition can be used to mitigate theoxygen inhibition of the free radical material. The molecular oxygen canquench the triplet state of a photoinitiator sensitizer or it canscavenge the free radicals resulting in reduced coating propertiesand/or uncured liquid surfaces. The oxygen inhibition mitigationcomposition can reduce the oxygen inhibition or can improve the cure ofany SLML.

The oxygen inhibition composition can comprise more than one compound.The oxygen inhibition mitigation composition can comprise at least oneacrylate, for example at least one acrylate monomer and at least oneacrylate oligomer. In an aspect, the oxygen inhibition mitigationcomposition can comprise at least one acrylate monomer and two acrylateoligomers. Non-limiting examples of an acrylate for use in the oxygeninhibition mitigation composition can include acrylates; methacrylates;epoxy acrylates, such as modified epoxy acrylate; polyester acrylates,such as acid functional polyester acrylates, tetra functional polyesteracrylates, modified polyester acrylates, and bio-sourced polyesteracrylates; polyether acrylates, such as amine modified polyetheracrylates including amine functional acrylate co-initiators and tertiaryamine co-initiators; urethane acrylates, such aromatic urethaneacrylates, modified aliphatic urethane acrylates, aliphatic urethaneacrylates, and aliphatic allophanate based urethane acrylates; andmonomers and oligomers thereof. In an aspect, the oxygen inhibitionmitigation composition can include at least one acrylate oligomer, suchas two oligomers. The at least one acrylate oligomer can beselected/chosen from a polyester acrylate and a polyether acrylate, suchas a mercapto modified polyester acrylate and an amine modifiedpolyether tetraacrylate. The oxygen inhibition mitigation compositioncan also include at least one monomer, such as 1,6-hexanedioldiacrylate. The oxygen inhibition mitigation composition can be presentin the first SLML in an amount ranging from about 5% to about 95%, forexample from about 10% to about 90%, and as a further example from about15% to about 85% by weight relative to the total weight of the SLML.

In some examples, the host material of the SLML can use a non-radicalcure system such as a cationic system. Cationic systems are lesssusceptible to the mitigation of the oxygen inhibition of the freeradical process, and thus may not require an oxygen inhibitionmitigation composition. In an example, the use of the monomer3-ethyl-3-hydroxymethyloxetane does not require an oxygen mitigationcomposition.

In an aspect, the first SLML can each independently include at least onephotoinitiator, such as two photoinitiators, or three photoinitiators.The photoinitiator can be used for shorter wavelengths. Thephotoinitiator can be active for actinic wavelength. The photoinitiatorcan be a Type 1 photoinitiator or a Type II photoinitiator. The SLML caninclude only Type I photoinitiators, only Type II photoinitiators, or acombination of both Type I and Type II photoinitiators. Thephotoinitiator can be present in the composition of the SLML in anamount ranging from about 0.25% to about 15%, for example from about0.5% to about 10%, and as a further example from about 1% to about 5% byweight relative to the total weight of the composition of the SLML.

The photoinitiator can be a phosphineoxide. The phosphineoxide caninclude, but is not limited to, a monoacyl phosphineoxide and a bis acylphosphine oxide. The mono acyl phosphine oxide can be a diphenyl(2,4,6-trimethylbenzoyl)phosphineoxide. The bis acyl phosphine oxide canbe a bis (2,4,6-trimethylbenzoyl)phenylphosphineoxide. In an aspect, atleast one phosphineoxide can be present in the composition of the SLML.For example, two phosphineoxides can be present in the composition ofthe SLM.

A sensitizer can be present in the composition of the SLML and can actas a sensitizer for Type 1 and/or a Type II photoinitiators. Thesensitizer can also act as a Type II photoinitiator. In an aspect, thesensitizer can be present in the composition of the SLML in an amountranging from about 0.05% to about 10%, for example from about 0.1% toabout 7%, and as a further example from about 1% to about 5% by weightrelative to the total weight of the composition of the SLML. Thesensitizer can be a thioxanthone, such as1-chloro-4-propoxythioxanthone.

In an aspect, the SLML can include a leveling agent. The leveling agentcan be a polyacrylate. The leveling agent can eliminate cratering of thecomposition of the SLML. The leveling agent can be present in thecomposition of the SLML in an amount ranging from about 0.05% to about10%, for example from about 1% to about 7%, and as a further examplefrom about 2% to about 5% by weight relative to the total weight of thecomposition of the SLML.

The first SLML can also include a defoamer. The defoamer can reducesurface tension. The defoamer can be a silicone free liquid organicpolymer. The defoamer can be present in the composition of the SLML inan amount ranging from about 0.05% to about 5%, for example from about0.2% to about 4%, and as a further example from about 0.4% to about 3%by weight relative to the total weight of the composition of the SLML.

The first SLML can each independently have a refractive index of greateror less than about 1.5. For example, each SLML can have a refractiveindex of approximately 1.5. The refractive index of each SLML can beselected to provide a degree of color travel required wherein colortravel can be defined as the change in hue angle measured in L*a*b*color space with the viewing angle. In some examples, each SLML caninclude a refractive index in a range of from about 1.1 to about 3.0,about 1.0 to about 1.3, or about 1.1 to about 1.2. In some examples, therefractive index of each SLML can be less than about 1.5, less thanabout 1.3, or less than about 1.2. In some examples, SLML can havesubstantially equal refractive indexes or different refractive indexesone from the other, if more than one SLML is present in the article.

The SLML can have a thickness ranging from about 1 nm to about 10000 nm,about 10 nm to about 1000 nm, about 20 nm to about 500 nm, about 1 nm,to about 100 nm, about 10 nm to about 1000 nm, about 1 nm to about 5000nm. In an aspect, the article, such as an optical device, can have anaspect ratio of 1:1 to 1:50 thickness to width.

One of the benefits of the article described herein, however, is that,in some examples, the optical effects appear relatively insensitive tothickness variations. Thus, in some aspects, each SLML can independentlyhave a variation in optical thickness of less than about 5%. In anaspect, each SLML can independently include an optical thicknessvariation of less than about 3% across the layer. In an aspect, eachSLML can independently have less than about 1% variation in opticalthickness across the layer having a thickness of about 50 nm.

FIGS. 1A-1D illustrates an article 10 including a layer 13 including atleast one color-rendering portion 14 and a least one light valve 12; anda metal reflector portion 16; wherein the at least one light valve 12 ispositioned in the layer 13 to provide reflection of incident lightthrough the at least one light valve 12. The layer 13 can be a firstlayer 13 and a second layer 13′, as shown in FIG. 1B. In an aspect, theat least one color-rendering portion 14 can be opaque, for examplewhite, black, or any color in the spectrum therebetween. Each of thefirst and second layers 13, 13′ can include at least one light valve 12.For example, each of the first and second layers 13, 13′ can include aplurality of light valves 12. The metal reflector portion 16 ispositioned between both of the first and second layer 13, 13′ so thatincident light can enter light valves 12 present in either first andsecond layers 13, 13′. FIGS. 1A, 1C, and 1D illustrate an asymmetricalarticle 10. FIG. 1B illustrated a symmetrical article 10. This canenable an article, such as a special effect pigment, to exhibit metallicsheen regardless of which side, i.e., first layer 13 or second layer 13′is facing away from a substrate coated with the article 10. FIGS. 1C and1D illustrate an article 10 with a transparent layer 20, which can belocated on at least one external surface of the article, such as eitherthe layer 13 and/or the metal reflector portion 16.

FIGS. 2A-2B illustrate an article 10 including a layer 13 including atleast one color-rendering portion 14 and at least one light valve 12;and a metal reflector portion 16. The at least one light valve 12 can bepositioned between the color-rendering portion 14 and the metalreflector portion 16, such as an at least one curved metal reflectorportion 16. The at least one light valve 12 can be a void area thatsurrounds and/or encapsulates the at least one curved metal reflectorportion 16. A thickness of the at least one light valve 12 can vary. Athin light valve 12 surrounding the at least one curved metal reflector16 can allow less incident light to pass through the light valve 12. Athicker light valve 12 surrounding the at least one curved metalreflector 16 can allow more incident light to pass through the lightvalve 12. In an aspect, the at least one curved metal reflector 16and/or the at least one light valve 12 can extend beyond a surface ofthe layer 13. In another aspect, the at least one curved metal reflectorportion 16 can extend through more than one surface of the layer 13. Forexample, the at least one curved metal reflector 16 can extend through aportion of a top surface of the layer 13. As a further example, the atleast one curved metal reflector 16 can extend through a portion of atop and bottom surface of the layer 13. As shown in FIG. 2B, the article10 can further include a transparent layer 20 as an external surface ofthe article 10. A transparent layer 20 can be present as every externalsurface of the article 10.

As shown in FIGS. 2A-2B, the at least one curved metal reflector 16 caninclude one or more, such as a plurality of, curved metal reflectors 16in the layer 13. If more than one curved metal reflector 16 is presentin the layer 13, then at least one curved metal reflector 16 can beencompassed and/or surrounded by at least one light valve 12. The atleast one-color-rendering portion 14 can be opaque.

FIGS. 3A-3E illustrate an article 10 including a layer 13 including atleast one color-rendering portion 14 and a least one light valve 12; anda metal reflector portion 16; wherein the at least one light valve 12 ispositioned in the layer 13 to provide reflection of incident lightthrough the at least one light valve 12. The at least onecolor-rendering portion 14 can be opaque. The layer 13 can be a first 13and a second layer 13′ with a metal reflector portion 16 positionedbetween them, as shown in FIGS. 3C-3E. The at least one light valve 12can include a transparent material. The transparent material can be atransparent bead. The transparent bead can be polystyrene or silica. Adiameter of the transparent bead can extend beyond a surface of thelayer 13, such as the first layer 13 and the second layer 13′. Inparticular, the at least one light valve 12 can be a bead having adiameter approximately equal to or larger than a height (thickness) of alayer 13, such as a first layer 13 and/or a second layer 13′. In anaspect, the transparent bead can be dissolved leaving a void area as theat least one light valve 12. The article 10 can also include atransparent layer 20 on an external surface of the article, as shown inFIGS. 3B, 3D, and 3E. FIG. 3E also illustrates a transparent layer 20,such as a third transparent layer 20″ and a fourth transparent layer 20″between the metal reflector portion 16 and the first and second layers13, 13′, respectively.

If more than one transparent layer 20 is present in the article 10, theneach transparent layer 20, 20′, 20″, and 20″' can be the same ordifferent, for example, in terms of composition, thickness, etc.Non-limiting examples of suitable transparent material for use in thetransparent layer 20 include a clear resin, polyacrylates,polymethacrylates, polystyrene, polyvinyl acetate, polyurethanes,polyvinyl chloride, polyvinyl alcohol, polyesters, polycarbonates,polyamides, polyimides, silicones, epoxy resins, their copolymers, etc.In an aspect, incident light can pass through the transparent layer 20and into the at least one light valve 12 in order to be reflected by themetal reflector portion 16.

FIGS. 4A-4D illustrate an article 10 including a layer 13 including atleast one color-rendering portion 14 and a least one light valve 12; anda metal reflector portion 16; wherein the at least one light valve 12 ispositioned in the layer 13 to provide reflection of incident lightthrough the at least one light valve 12. The layer 13 can be a firstlayer 13 and a second layer 13′, as shown in FIGS. 4C-4D. In an aspect,the at least one color-rendering portion 14 can be opaque, for examplewhite, black, or any color in the spectrum therebetween. The at leastone color-rendering portion 14 can be beads. Each of the first andsecond layers 13, 13′ can include a plurality of color-renderingportions 14 spaced throughout the layers 13, 13′. Each of the first andsecond layers 13, 13′ include at least one light valve 12. For example,each of the first and second layers 13, 13′ include a plurality of lightvalves 12. The metal reflector portion 16 can be positioned between bothof the first and second layer 13, 13′ so that incident light can enterlight valves 12 present in either first and second layers 13, 13′. Thearticle 10 can be asymmetrical, as shown in FIGS. 4A and 4B, or can besymmetrical, as shown in FIGS. 4C and 4D. A symmetrical article 10, suchas a special effect pigment, can exhibit metallic sheen regardless ofwhich side, i.e., first layer 13 or second layer 13′ is facing away froma substrate coated with the article 10.

FIGS. 4B and 4D illustrate an article 10 further including a transparentlayer 20, such as first, second, third, and fourth transparent layers20, 20′, 20″, and 20″′. The transparent layer can also be present oneither side of the metal reflector portion 16.

In an aspect, the article 10, such as an optical device in the form of aflake, foil or sheet, can also include a substrate and/or a releaselayer. In an aspect, the release layer can be disposed between asubstrate and the article 10. The substrate can be made of a flexiblematerial. The substrate can be any suitable material that can receivelayers deposited during the manufacturing process. Non-limiting examplesof suitable substrate materials include polymer web, such aspolyethylene terephthalate (PET), glass foil, glass sheets, polymericfoils, polymeric sheets, metal foils, metal sheets, ceramic foils,ceramic sheets, ionic liquid, paper, silicon wafers, etc. The substratecan vary in thickness, but can range for example from about 2 μm toabout 100 μm, and as a further example from about 10 to about 50 μm.

Additionally, or alternatively, the article 10, in the form of a flake,sheet, or foil, can also include a hard coat or protective layer. Insome examples, these layers (hard coat or protective layer) do notrequire optical qualities.

The article 10, such as optical devices, described herein can be made inany way. For example, successive layers can be deposited forming asheet, which can then be divided, broken, ground, etc. into smallerpieces thereby forming an article 10. In some examples, the sheet can becreated by a liquid coating process, alone or in combination withdeposition techniques.

There is disclosed a method for manufacturing an article 10, for examplein the form of a sheet, flake, or foil, as described herein. The methodcan include successively depositing layers onto the substrate to formthe article 10. The deposited layers can include one or more of thefollowing layers in any order: a layer 13 including at least onecolor-rendering portion 14 and at least one light valve 12 (such as aselective light modulator layer), a reflector portion 16, a magneticlayer, a dielectric stack, a transparent layer 20, and an absorberlayer.

The method can comprise coating a first layer 13 having at least onecolor-rendering portion 14 and at least one light valve 12 onto asubstrate, for example using a liquid coating process. A metal reflectorportion 16 can be deposited onto the first layer 13. In the disclosedmethods, the metal reflector portion 16 can be deposited usingdeposition process, such as physical vapor deposition, chemical vapordeposition, thin-film deposition, atomic layer deposition, etc.,including modified techniques such as plasma enhanced and fluidized bed.This method

A second layer 13′ including at least one color-rendering portion 14 andat least one light valve 12 can be coated onto the metal reflectorportion 16. As previously discussed, the first layer 13 and the secondlayer 13′ can be the same or different.

The layer 13, such as a first layer 13 and a second layer 13′, can bedeposited by a liquid coating process, such as a slot die process. Theliquid coating process can include, but is not limited to: slot-bead,slide bead, slot curtain, slide curtain, in single and multilayercoating, tensioned web slot, gravure, roll coating, and other liquidcoating and printing processes that apply a liquid on to a substrate orpreviously deposited layer to form a liquid layer or film that issubsequently dried and/or cured.

The substrate can be released from the deposited layers (including, butnot limited to a reflector portion 16, and layer 13) to create thearticle 10. In an aspect, the substrate can be cooled to embrittle anassociated release layer, if present. In another aspect, the releaselayer could be embrittled for example by heating and/or curing withphotonic or e-beam energy, to increase the degree of cross-linking,which would enable stripping. The deposited layers can then be strippedmechanically, such as sharp bending or brushing of the surface. Thereleased and stripped layers can be sized into article 10, such as anoptical device in the form of a flake, foil, or sheet, using knowntechniques.

In another aspect, the deposited layers can be transferred from thesubstrate to another surface. The deposited layers can be punched or cutto produce large flakes with well-defined sizes and shapes.

The liquid coating process can allow for the transfer of the compositionof the SLML (such as the layer 13) at a faster rate as compared to otherdeposition techniques, such as vapor deposition. Additionally, theliquid coating process can allow for a wider variety of materials to beused in the SLML with a simple equipment set up. It is believed that theSLML formed using the disclosed liquid coating process can exhibitimproved optical performance.

A liquid coating process can include inserting into a slot die acomposition of a layer, e.g. SLML (a liquid coating composition) anddepositing the composition on a substrate resulting in a wet film. Withreference to the processes disclosed above, the substrate can include atleast one of a substrate, a release layer, a reflector layer, andpreviously deposited layers. The distance from the bottom of the slotdie to the substrate is the slot gap G. The liquid coating compositioncan be deposited at a wet film thickness D that is greater than a dryfilm thickness H. After the wet film of the liquid coating compositionhas been deposited on the substrate, any solvent present in the wet filmof the liquid coating composition can be evaporated. The liquid coatingprocess continues with curing of the wet film of the liquid coatingcomposition to result in a cured, self-leveled layer having the correctoptical thickness H (ranging from about 30 to about 700 nm). It isbelieved that the ability of the liquid coating composition toself-level results in a layer having a reduced optical thicknessvariation across the layer. Ultimately, an article, such as an opticaldevice, comprising the self-leveled liquid coating composition canexhibit increased optical precision. For ease of understanding, theterms “wet film” and “dry film” will be used to refer to the liquidcoating composition at various stages of the liquid coating process.

The liquid coating process can comprise adjusting at least one of acoating speed and a slot gap G to achieve a wet film with apredetermined thickness D. The liquid coating composition can bedeposited having a wet film thickness D ranging from about 0.1 μm toabout 500 μm, for example from about 0.1 μm to about 5 μm. The liquidcoating composition formed with a wet film thickness D in the disclosedrange can result in a stable SLML layer, such as a dielectric layer,i.e., without breaks or defects such as ribbing or streaks. In anaspect, the wet film can have a thickness of about 10 μm for a stablewet film using a slot die bead mode with a coating speed up to about 100m/min. In another aspect, the wet film can have a thickness of about 6-7μm for a stable wet film using a slot die curtain mode with a coatingspeed up to about 1200 m/min.

The liquid coating process can include a ratio of slot gap G to wet filmthickness D of about 1 to about 100 at speeds from about 0.1 to about1000 m/min. In an aspect, the ratio is about 9 at a coating speed ofabout 100 m/min. In an aspect, the ratio can be about 20 at a coatingspeed of about 50 m/min. The liquid coating process can have a slot gapG ranging from about 0 to about 1000 μm. A smaller slot gap G can allowfor a reduced wet film thickness. In slot-bead mode higher coatingspeeds can be achieved with a wet film thickness greater than 10 μm.

The liquid coating process can have a coating speed ranging from about0.1 to about 1000 m/min, for example from about 25 m/min to about 950m/min, for example from about 100 m/min to about 900 m/min, and as afurther example from about 200 m/min to about 850 m/min. In an aspect,the coating speed is greater than about 150 m/min, and in a furtherexample is greater than about 500 m/min.

In an aspect, the coating speed for a bead mode liquid coating processcan range from about 0.1 m/min to about 600 m/min, and for example fromabout 50 to about 150 m/min. In another aspect, the coating speed for acurtain mode liquid coating process can range from about 200 m/min toabout 1500 m/min, and for example, from about 300 m/min to about 1200m/min.

The solvent can be evaporated from the wet film, such as before the wetfilm is cured. In an aspect, about 100%, for example about 99.9%, and asa further example about 99.8% of the solvent can be evaporated from theliquid coating composition prior to curing of the liquid coatingcomposition. In a further aspect, trace amounts of solvent can bepresent in a cured/dry liquid coating composition. In an aspect, a wetfilm having a greater original weight percent of solvent can result in adry film having a reduced film thickness H. In particular, a wet filmhaving a high weight percent of solvent and being deposited at a highwet film thickness D can result in a liquid coating composition, such asthe SLML having a low dry film thickness H. It is important to note,that after evaporation of the solvent, the wet film remains a liquidthereby avoiding problems such as skinning, and island formation duringthe subsequent curing steps in the liquid coating process.

The dynamic viscosity of the wet film can range from about 0.5 to about50 cP, for example from about 1 to about 45 cP, and as a further examplefrom about 2 to about 40 cP. The viscosity measurement temperature is25° C. The rheology was measured with an Anton Paar MCR 101 rheometerequipped with a solvent trap using a cone/plate 40 mm diameter with 0.3°angle at a gap setting of 0.025 mm.

In an aspect, the liquid coating composition and the solvent can beselected so that the wet film exhibits Newtonian behavior for precisioncoating of the liquid coating composition using the liquid coatingprocess. The wet film can exhibit Newtonian behavior shear rates up to10,000 s⁻¹ and higher. In an aspect, the shear rate for the liquidcoating process can be 1000 s⁻¹ for a coating speed up to 25 m/min, forexample 3900 s⁻¹ for a coating speed up to 100 m/min, and as a furtherexample 7900 s⁻¹ for a coating speed up to 200 m/min. It will beunderstood that a maximum shear rate can occur on a very thin wet film,such as 1 μm thick.

As the wet film thickness is increased, the shear rate can be expectedto decrease, for example decrease 15% for a 10 μm wet film, and as afurther example decrease 30% for a 20 μm wet film.

The evaporation of the solvent from the wet film can cause a change inviscosity behavior to pseudoplastic, which can be beneficial to achievea precision SLML. The dynamic viscosity of the deposited SLML after anysolvent has been evaporated, can range from about 10 cP to about 3000cP, for example from about 20 cP to about 2500 cP, and as a furtherexample from about 30 cP to about 2000 cP. When evaporating the solvent,if present, from the wet film there can be an increase in viscosity tothe pseudoplastic behavior. The pseudoplastic behavior can allow forself-leveling of the wet film.

In an aspect, the method can include evaporating the solvent present inthe wet film using known techniques. The amount of time required toevaporate the solvent can be dependent upon the speed of theweb/substrate and the dryer capacity. In an aspect, the temperature ofthe dryer (not shown) can be less than about 120° C., for example lessthan about 100° C., and as a further example less than about 80° C.

The wet film deposited using a liquid coating process can be cured usingknown techniques. For example, the disclosed methods can further includecuring or hardening the coated first layer 13 before depositing themetal reflector portion 16. In another aspect, the method can furtherinclude curing or hardening the coated second layer 13′. In an aspect,the wet film, i.e., an SLML such as the layer 13, can be cured using acuring agent utilizing at least one of an ultraviolet light, visiblelight, infrared, or electron beam. Curing can proceed in an inert orambient atmosphere. In an aspect, the curing step utilizes anultraviolet light source having a wavelength of about 395 nm. Theultraviolet light source can be applied to the wet film at a doseranging from about 200 mJ/cm² to about 1000 mJ/cm², for example rangingfrom about 250 mJ/cm² to about 900 mJ/cm², and as a further example fromabout 300 mJ/cm² to about 850 mJ/cm².

The wet film can crosslink by known techniques. Non-limiting examplesinclude photoinduced polymerization, such as free radicalpolymerization, spectrally sensitized photoinduced free radicalpolymerization, photoinduced cationic polymerization, spectrallysensitized photoinduced cationic polymerization, and photoinducedcycloaddition; electron beam induced polymerization, such as electronbeam induced free radical polymerization, electron beam induced cationicpolymerization, and electron beam induced cycloaddition; and thermallyinduced polymerization, such as thermally induced cationicpolymerization.

A SLML formed using the liquid coating process can exhibit improvedoptical performance, i.e., be a precision SLML. In some examples, aprecision SLML can be understood to mean a SLML having less than about3% optical thickness variation, about 5% optical thickness variation, orabout 7% optical thickness variation across the layer.

In an aspect, the liquid coating process can include adjusting at leastone of speed from about 5 to about 100 m/min and a coating gap fromabout 50 μm to about 100 μm to deposit a wet film from about 2 μm to 10μm of the selective light modulator layer with a predetermined thicknessfrom about 500 nm to about 1500 nm. In a further aspect, the process caninclude a speed of 30m/min, a 75 um gap, 10 um wet film, dry filmthickness 1.25 um.

In the disclosed method, the at least one light valve 12 can be a bead,and the method can further include dissolving the bead to form a voidarea in the layer 13. The method can also include filling the void areawith a transparent material, which can be the same or differenttransparent material used to form the disclosed transparent layer 20.

In an aspect, the method can further include coating a first transparentlayer 20 between the substrate and the first layer 13. The method canalso further include coating a second transparent layer 20′ onto thecoated second layer 13′. The method can further include coating a thirdtransparent layer 20″ between the first layer 13 and the metal reflectorportion 16. The method can further include coating a fourth transparentlayer 20″′ between the second layer 13′ and the metal reflector portion16.

The first and second layers 13, 13′ can be cured and/or cross-linked asdisclosed above before any additional layers are deposited on them. Thefirst and second layers 13, 13′ can be coated using the disclosed liquidcoating processes. The transparent layers 20, 20′, 20″, and 20″′, andthe metal reflector portion 16 can be deposited using the discloseddeposition techniques. The transparent layers 20, 20′, 20″, and 20″′ canbe coated using a liquid coating process. The transparent layers canprovide a smooth outer surface to the article 10. In yet another aspect,the method can further include coating a third transparent layer 20″between the first layer 13 and the metal reflector portion 16. Themethod can further include coating a fourth transparent layer 20″′between the second layer 13′ and the metal reflector portion 16.

In an aspect, the at least one light valve 12 present in the first andsecond layers 13, 13′ can be a bead having a diameter equal to or largerthan a height (thickness) of the first and second layers 13, 13′.

From the foregoing description, those skilled in the art can appreciatethat the present teachings can be implemented in a variety of forms.Therefore, while these teachings have been described in connection withparticular embodiments and examples thereof, the true scope of thepresent teachings should not be so limited. Various changes andmodifications can be made without departing from the scope of theteachings herein.

This scope disclosure is to be broadly construed. It is intended thatthis disclosure disclose equivalents, means, systems and methods toachieve the devices, activities and mechanical actions disclosed herein.For each device, article, method, mean, mechanical element or mechanismdisclosed, it is intended that this disclosure also encompass in itsdisclosure and teaches equivalents, means, systems and methods forpracticing the many aspects, mechanisms and devices disclosed herein.Additionally, this disclosure regards a coating and its many aspects,features and elements. Such a device can be dynamic in its use andoperation, this disclosure is intended to encompass the equivalents,means, systems and methods of the use of the device and/or opticaldevice of manufacture and its many aspects consistent with thedescription and spirit of the operations and functions disclosed herein.The claims of this application are likewise to be broadly construed. Thedescription of the inventions herein in their many embodiments is merelyexemplary in nature and, thus, variations that do not depart from thegist of the invention are intended to be within the scope of theinvention. Such variations are not to be regarded as a departure fromthe spirit and scope of the invention.

1. An article, comprising: a valve layer including at least onecolor-rendering portion and at least one light valve; and a metalreflector portion; wherein the at least one light valve is positioned inthe valve layer to provide reflection of incident light through the atleast one light valve.
 2. The article of claim 1, wherein articleincludes only a single valve layer.
 3. The article of claim 1, whereinat least one color-rendering portion is opaque.
 4. The article of claim1, wherein the at least one color-rendering portion comprises lightabsorbing or light scattering materials.
 5. The article of claim 1,wherein the at least one color-rendering portion comprises at least oneof dyes and colorants.
 6. The article of claim 1, wherein the valvelayer is a selective light modulator layer.
 7. The article of claim 1,wherein the at least one light valve is dimensioned to allow incidentlight to pass through the at least one light valve.
 8. The article ofclaim 1, wherein the at least one light valve is a void area in thevalve layer.
 9. The article of claim 1, wherein the at least one lightvalve is an optical pathway through which incident light reaches themetal reflector portion.
 10. The article of claim 1, wherein the atleast one light valve is a plurality of light valves spaced throughoutthe valve layer.
 11. The article of claim 1, wherein the at least onelight valve is a three-dimensional shape with flat polygonal faces. 12.The article of claim 1, wherein the at least one light valve is athree-dimensional round shape.
 13. The article of claim 1, wherein theat least one light valve can be at least the same height as the valvelayer.
 14. The article of claim 1, wherein a portion of the at least onelight valve can extend above a surface of the valve layer.
 15. Thearticle of claim 1, wherein the at least one light valve is a beadcomprised of transparent material with a defined geometry.
 16. Thearticle of claim 15, wherein a diameter of the bead is greater than orequal to a height of the valve layer.
 17. The article of claim 1,wherein the metal reflector portion is at least one curved metalreflector.
 18. A method for making an article, comprising: coating avalve layer having at least one light valve and at least onecolor-rendering portion onto a substrate; and depositing a metalreflector portion onto the valve layer.
 19. The method of claim 18,further comprising curing or hardening the coated valve layer beforedepositing the metal reflector portion.
 20. The method of claim 18,wherein the at least one light valve is a bead; and the method furthercomprises dissolving the bead to form a void area; and filling the voidarea with a transparent material.
 21. The method of claim 18, furthercomprising coating a first transparent layer, the first transparentlayer being on the valve layer when the article is completed.